WO1999026985A1 - Polymerization catalyst for olefin monomers - Google Patents

Polymerization catalyst for olefin monomers Download PDF

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Publication number
WO1999026985A1
WO1999026985A1 PCT/KR1998/000375 KR9800375W WO9926985A1 WO 1999026985 A1 WO1999026985 A1 WO 1999026985A1 KR 9800375 W KR9800375 W KR 9800375W WO 9926985 A1 WO9926985 A1 WO 9926985A1
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Prior art keywords
bis
methyl
ethane
carbon atoms
indenyl
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PCT/KR1998/000375
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French (fr)
Inventor
Jae-Seung Oh
Jae-Hyeon Park
Young-Whan Park
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Lg Chemical Ltd.
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Publication date
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Priority to EP98959229A priority Critical patent/EP1034190B1/en
Priority to JP2000522140A priority patent/JP2001524492A/en
Priority to AT98959229T priority patent/ATE248194T1/en
Priority to DE69817603T priority patent/DE69817603T2/en
Publication of WO1999026985A1 publication Critical patent/WO1999026985A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
    • C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound

Abstract

Transition metal compounds coordinated with bis-cyclopentadienyl type ligands, in which steric hindrance is given to the central metal and the direction of steric hindrance is controlled, not by connection cyclopentadienyl moities directly with diradical as in previous arts, but by selecting appropriate number of atoms and location of bridge-bonding as shown in formula (X) and (XI) where R1 - R6 are respectively same or different substituent containing 1 - 20 non-hydrogen atoms.

Description

POLYMERIZATION CATALYST FOR OLEFIN MONOMERS
a) Field of the invention
This invention relates to catalyst for the homo- or co-polymerization of ethylene, α -oldfin and cyclooldfin. More particularly, this invention related to the structure of the transition metal compounds which can be used for the homo- or co-polymerization of ethylene, a -oldfin and cyclooldfin.
b) Background of the invention In the early 1980s, Prof. Kaminsky reported in DE 3127133 that the metallocene compound of group IV showed excellent activity in the olefin polymerization when it was activated with alkylaluminoxane. Since that, active research was done to develop the novel catalysts by varing the structure of the cyclopentadienyl ligands. Metallocene compounds whose two cyclopentadienyl or hydroindenyl or fiuorenyl ligands was connected by bridge (bridged metallocene compounds) was synthesized and tested for the polymerization to show characteristic reacticity which could not be seen with unbridged metallocene compounds. For example, C2 symmetric bridged metallocene compounds containing two (hydro)indenyl lignads gave isotactic steroselectivity in the a - oldfin polymerization (DE 3508887, EP-A-485821 , EP-A-485823). However, the meso-compounds, which have the same composition but have different symmetry, Cs, was known to give a uniform comonomer composition in the polymer chains when it was used for the copoymerization of cycloolefin and ethylene or a -oldfin (DE 4107682).
The metallocene compound which was derived from bridged ligand of cyclopentadienyl and fiuorenyl showed the syndiotactic stereoselectivty in the a -olefin polymerization (EP-A-351392). The bridge connect directly two five membered ring of the cyclopentadienyl or indenyl or hydroindenyl or fiuorenyl ligands via methylene, ethylene, and dialkylsilylene diradical in the previously known bridged metallocene compounds. R. H. Halterman summarize it in Chemical Review, 92, 659 (1992).
5 BRIEF DESCRIPTION OF THE INVENTION
This invention gives the novel structure of the bridged transition metal compounds in which the bridge connect the two ligands in different way.
The bridge connect indirectly the two cyclopentadienyl rings. That is,
10 the cyclopentadienyl ligands whose two adjacent carbon were connected by triradicals to form annulated cyclopentadienyl ligand containing one radical in a newly formed ring are bridged by connecting each said remaining one radical to bridge. Novel bridged metallocene compounds can be synthesized by this bridged ligands.
15 In previous bridged metallocene compounds, steric hindrance was endowed by the annulated ring of the cyclopentadienyl ligands.
The metallocene compounds described in this invention endow the different steric hindrance from previously known bridged metallocene compounds, and especially the steric hindrance can be controlled by changing
20 the length of bridge and bridging point.
In rac-ethylenebis(indenyl)zirconium dichloride, there is two conformational fluxional motion, Yform and Λ -form (Organometaliics, 14, 1256 (1995)). This motion was known to decrease the stereoselcetivity in the a -olefin polymerization at high temperature (Metaliocenes x95 proceedings
25 403f and references sited therein). A bridged metallocene depicted in this invention, for example, rac-metallocene compound in which two indenyl ligand was connected by ethylene through 6 position of the indenyl ring cannot have such a conformational fluxtional motion.
It has been impossible to prepare exclusively meso-compound in the
30 synthesis of the previously known bridged compounds. For example, S. Collins and R. B. Raush reported respectively in Journal of Organometallic Chemistry, vol. 342, 21 (1998) and Organometallics, vol. 10, 1501 (1991) that the rac- and meso-compounds are almost always obtained as a mixture and tedious separation step is necessary. Furthermore, because the meso- compound is usually minor isomer, it is not suitable to use meso isomer in industry. In this invention are disclosed novel structures of bridged ligands that give only meso isomers due to their stererochemistry and their novel bridged metallocene compounds.
DETAILED DESCRIPTION OF THE INVENTION
This invention related to the transition metal compounds represented general structure (I):
Figure imgf000005_0001
Where M is a transition metal selected from of Group 3 or 4 or 5 or 6.
A1 and A2 are respectively and independently hydrocarbyl triradical consisted of more than two carbon atoms which are bonded to the cyclopetadienyl ring in covalently, or 0 - 10 carbon atoms including one or more of B, N, P, S, O, or Si atom, in which the triradical may have same or different substiuents containing 1 - 20 non-hydrogen atoms.
B is hydrocarbyl diradical containing 1 - 20 carbon atoms or substituted hydrocarbyl diradical containing 0 - 20 carbon atoms, B, N, P, S, O, or Si atoms in which the diradical may have same or different substituents containing 1 - 20 non-hydrogen atoms and the radicals joined to C1 and C2 to form bridge by covalent bonds.
C1 and C2 are respectively and independently triradical of cyclopentadienyl moity which is covalently bonded to two radical sites of A1 and A2 and one radical site of M, in which the triradical may have same or different substituents containing 1 - 20 non-hydrogen atoms and the substituent may be hydrocarbyl radical with 1 - 20 carbon atoms or radical containing one or more of B, N, P, S, O, or Si atoms and 1 - 20 carbon atoms.
X is respectively and independently ligand of halogen, hydrocarbyl containing 1 - 20 carbon atoms, alkoxy, aryloxy, amide, arylamide, phosphide, arylphosphide, sulfide, or arylsulfide. n is integer of 0 - 4 which depends on the oxidation state of M.
In above general formula (I), M can be, particularly, Ti, Zr, Hf, Sc, Cr, V, W and, more particularly, Ti, Zr, Hf. Illustrative but not limiting example of bridged cyclopentadienyl ligands (R1-A1-B-A2-R2) are bis(4-indenyl)methane, bis(5- indenyl)methane, bis(7-indenyl)methane, bis(1-fluorenyl)methane, bis(2- fluorenyl)methane, bis(3-fluorenyl)methane, bis(4-fluorenyl)methane, bis(4-(2)- indenyl)methane, bis(5-(2)-indenyl)methane, bis(5-(2)-indenyl)methane, bis(6-
(2)-indenyl)methane, bis(7-(2)-indenyl)methane, bis(4-(1 )-indenyl)methane, bis(5-(1-methyl)indenyl)methan, bis(6-(1-methyl)indenyl)methan, bis(7-(1- methyl) ndenyl)methan, bis(4-(3-methyl) ndenyl)methan, bis(5-(3- methyl) ndenyl)methan, bis(6-(3-methyl) ndenyl)methan, bis(7-(3- methyl) ndenyhmethan, bis(4-(5-methyl) ndenyl)methan, bis(5-(6- methyl) ndenyl)methan, bis(6-(5-methyl) ndenyl)methan, bis(7-(5- methyl) ndenyl)methan, bis(4-(6-methyl) ιndenyl)methan, bis(5-(4- methyl) ndenyl)methan, bis(6-(4-methyl) ndenyl)methan, bis(7-(4- methyl) ndenyl)methan, bis(4-(6-methyl) indenyl)methan, bis(5-(7- methyl) ndenyl)methan, bis(6-(7-methyl)i indenyl)methan, bis(7-(6- methyl) ndenyl)methan, bis(4-(7-methy ll)indenyl)methan, (4-(7- methyl)indenyl)(7-(4-methyl)indenyl)methan, (4-(7-methyl)indenyl)(5-(4- methyl)indenyl)methan, (4-(7-methyl)indenyl)(6-(4-methyl)indenyl)methan, bis(4-(2,5-dimethyl)indenyl)methan, bis(4-(2,6-dimethyl)indenyl)methan, bis(4- (2,7-dimethyl)indenyl)methan, bis(4-(1 ,5-dimethyl)indenyl)methan, bis(4-(1 ,6- dimethyl)indenyl)methan, bis(4-(1 ,2-dimethyl)indenyl)methan, bis(4-(2,3- dimethyl)indenyl)methan, bis(4-(5,6-dimethyl)indenyl)methan, bis(4-(5,7- dimethyl)indenyl)methan, bis(4-(6,7-dimethyl)indenyl)methan, bis(7-(2,5- dimethyl)indenyl)methan, bis(7-(1 ,5-dimethyl)indenyl)methan, bis(7-(1 ,6- dimethyl)indenyl)methan, bis(7-(1 ,2-dimethyl)indenyl)methan, bis(7-(2,3- dimethyl)indenyl)methan, bis(7-(5,6-dimethyl)indenyl)methan, bis(7-(4,5- dimethyl)indenyl)methan, bis(7-(4,6-dimethyl)indenyl)methan, (4-(2,7- dimethyl)indenyl)(7-(2,4-dimethyl)indenyl)methan, 1 ,2-bis(4-indenyl)ethane,
1 ,2-bis(5-indenyl)ethane, 1 ,2-bis(5-indenyl)ethane, 1 ,2-bis(7-indenyl)ethane, bis(4-(7-methyl)indenyl)ethane, (4-(7-methyl)indenyl) (7-(4- methyl)indenyl)ethane, (4-(7-methyl)indenyl) (5-(4-methyl)indenyl)ethane, (4-
(7-methyl)indenyl) (6-(4-methyl)indenyl)ethane, bis(4-(2-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(5-(2-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(6-(2-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(7-(2-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(4-(1-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(5-(1-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(6-(1-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(7-(1-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(4-(3-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(5-(3-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(6-(3-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(7-(3-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(4-(5-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(5-(6-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(6-(5-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(7-(5-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(4-(6-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(4-(2-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(5-(4-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(6-(4-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(7-(4-methyl)-4, 5,6,7- tetrahydroindenyl)methane, bis(4-(6-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(5-(7-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(6-(7-methyl )-4,5,6,7- tetrahydroindenyl)methane, bis(7-(6-methyl H,5,6,7- tetrahydroindenyl)methane, s(4-( 2,5-dι methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 2,6-dι methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 2,7-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 1 ,5-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 1 ,6-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 1 ,2-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 2,3-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 5,6-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(4-( 5,7-d methyl H.5,6,7- tetrahydro ndenyl)methane, s(4-( 6,7-d methyl H,5,6,7- tetrahydro ndenyl)methane, s(7-< :2,5-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(7-l ;2,6-d methyl H.5,6,7- tetrahydro ndenyl)methane, s(7- [2,4-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(7- [1 ,5-d methyl H.5,6,7- tetrahydro ndenyl)methane, s(7- (1 ,6-d methyl H,5,6,7- tetrahydro ndenyl)methane, s(7- (1 ,2-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, s(7- (2,3-d methyl H.5,6,7- tetrahydro ndenyl)methane, s(7- (5,6-d methyl H.5,6,7- tetrahydro ndenyl)methane, s(7- (4,5-d methyl H,5,6,7- tetrahydro ndenyl)methane, s(7- (4,6-d methyl )-4,5,6,7- tetrahydro ndenyl)methane, 1 ,2-bis(4-4,5,6,7-tetrahydroindenyl)ethane, 1 ,2- bis(5-4,5,6,7-tetrahydroindenyl)ethane, 1 ,2-bis(6-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(7-4,5,6,7-tetrahydroindenyl)ethane, 1 ,3- bis(1-fluorenyl)propane, 1 ,2-bis(2-fluorenyl)ethane, 1 ,2-bis(3-fluorenyl)ethane, 1 ,2-bis(4-fluorenyl)ethane, 1 ,2-bis(4-(2-methyl)indenyl)ethane, 1 ,2-bis(5-(2- methyl)indenyl)ethane, 1 ,2-bis(6-(2-methyl)indenyl)methane, 1 ,2-bis(7-(2- methyl)indenyl)ethane, 1 ,2-bis(4-(1-methyl)indenyl)ethane, 1 ,2-bis(5-(1- methyl)indenyl)methane, 1 ,2-bis(6-(1-methyl)indenyl)methane, 1 ,2-bis(7-(1- methyl)indenyl)ethane, 1 ,2-bis(4-(3-methyl)indenyl)ethane, 1 ,2-bis(5-(3- methyl)indenyl)ethane, 1 ,2-bis(6-(3-methyl)indenyl)ethane, 1 ,2-bis(7-(3- methyl)indenyl)ethane, 1 ,2-bis(4-(5-methyl)indenyl)ethane, 1 ,2-bis(5-(6- methyl)indenyl)ethane, 1 ,2-bis(6-(5-methyl)indenyl)ethane, 1 ,2-bis(7-(5- methyl)indenyl)ethane, 1 ,2-bis(4-(6-methyl)indenyl)ethane, 1 ,2-bis(5-(7- methyl)indenyl)ethane, 1 ,2-bis(6-(7-methyl)indenyl)ethane, 1 ,2-bis(7-(6- methyl)indenyl)ethane, 1 ,2-bis(4-(2,5-dimethyl)indenyl)ethane, 1 ,2-bis(4-(2,6- dimethyl)indenyl)ethane, 1 ,2-bis(4-(2,7-dimethyl)indenyl)ethane, 1 ,2-bis(4- (1 ,5-dimethyl)indenyl)ethane, 1 ,2-bis(4-(1 ,6-dimethyl)indenyl)ethane, 1 ,2- bis(4-(1 ,2-dimethyl)indenyl)ethane, 1 ,3-bis(4-(2,3-dimethyl)propane, 1 ,2-bis(4- (5,6-dimethyl)indenyl)ethane, 1 ,2-bis(4-(5,7-dimethyl)indenyl)ethane, 1 ,2- bis(4-(6,7-dimethyl)indenyl)ethane, 1 ,2-bis(5- -(2,3-dimethy ndenyl )ethane,
1 ,2-bis(-(2,6-dimethyl) ndenyl)ethane, 1 ,2-bis(5 -(2,4-dimethy ndenyl )ethane,
1 ,2-bis(5 (1,2-dimethy ndenyl) )ethane, 1 ,2-bis(5 -(1 ,3-dimethy ndenyl )ethane, 1,2-bis(5 (1,4-dimethy ndenyl) )ethane, 1 ,2-bis(5 -(2,3-dimethy ndenyl )ethane, 1,2-bis(5 (4,6-dimethy ndenyl) )ethane, 1 ,2-bis(5 -(4,7-dimethy ndenyl )ethane, 1,2-bis(5 (3,6-dimethy ndenyl) )ethane, 1 ,2-bis(5 -(3,7-dimethy ndenyl )ethane, 1,2-bis(6 (2,5-dimethy ndenyl) )ethane, 1 ,2-bis(6 -(2,4-dimethy ndenyl )ethane, 1 ,2-bis(6-(2,3-dimethy ndenyl) )ethane, 1 ,2-bis(6 -(1 ,5-dimethy ndenyl )ethane, 1,2-bis(6 (1,3-dimethy ndenyl) )ethane, 1 ,2-bis(6 -(1 ,2-dimethy ndenyl )ethane, 1,2-bis(6 (5,7-dimethy ndenyl) )ethane, 1 ,2-bis(6 -(4,5-dimethy ndenyl )ethane, 1,2-bis(6 (1,4-dimethy ndenyl) )ethane, 1 ,2-bis(7 -(2,5-dimethy ndenyl )ethane, 1 ,2-bis(7-(2,6-dimethy ndenyl) )ethane, 1 ,2-bis(7- -(2,4-dimethy ndenyl )ethane, 1 ,2-bis(7 (1,5-dimethy ndenyl) )ethane, 1 ,2-bis(7 -(1 ,6-dimethy ndenyl )ethane, 1,2-bis(7 (1,2-dimethy ndenyl) )ethane, 1 ,2-bis(7 -(2,3-dimethy ndenyl )ethane, 1,2-bis(7 (5,6-dimethy ndenyl) )ethane, 1 ,2-bis(7- -(4,5-dimethy ndenyl )ethane, 1 ,2-bis(7 (4,6-dimethy ndenyl) )ethane, bis-(4-(1 ,2,3-trimethyl)indenyl)methane, bis-(7-(1,2,4-trimethyl) ndenyl)methane, 1 ,2-bis-(7-(1 ,2,4- trimethyl)indenyl)methane, bis-(4-(1 ,2,7-trimethyl)indenyi)methane, bis-(4-
(1 ,3,5-trimethyl)indenyl)methane, 1 ,2-bis-(5-(1 ,2,4-trimethyl)indenyl)methane, 1 ,2-bis-(6-(1 ,2,3-trimethyl)indenyl)methane, 1 ,2-bis-(7-(4,5,6- trimethyl)indenyl)methane, 1 ,3-bis-(4-(5,6,7-trimethyl)indenyl)propane, 1 ,2-bis- (6-(4,5,7-trimethyl)indenyl)ethane, 1 ,2-bis-(5-(4,6,7-trimethyl)indenyl)ethane, bis-(4-(5,6,7-trimethyl)indenyl)methane, bis-(4-(1 ,2,3,5- tetramethyl)indenyl)methane, bis-(7-(1 ,2,3,4-tetramethyl)indenyl)methane,
1 ,2-bis-(7-(1 ,2,3,4-tetramethyl)indenyl)ethane, bis-(4-(2, 5,6,7- tetramethyl)indenyl)methane, bis-(4-(1 ,3,5,6-tetramethyi)indenyl)methane, 1 ,2- bis-(5-(1 ,2,3,4-tetramethyl)indenyl)methane, 1 ,2-bis-(6-(1 ,2,3,4- tetramethyl)indenyl)methane, 1,2-bis-(7-(2,4,5,6-tetramethyl)indenyl)methane,
1 ,2-bis-(4-(2,5,6,7-tetramethyl)indenyl)methane, 1 ,2-bis-(6-(3,4,5,7- tetramethyl)indenyl)methane, 1 ,2-bis-(5-(1 ,4,6,7-tetramethyl)indenyl)methane, 1 ,2-bis-(4-(1 ,5,6,7-tetramethyl)indenyl)methane, (4-indenyl)(4-(1- methyl)indenyl)methane, bis(4-indenyl)methylmethane, bis(4-(2- methyl)indenyl)dimethyimethane, (4-fluorenyl)(4-indenyl)methane, 1 -,2-bis(5- indenyl)-1 ,2-dimethylethane, 1 ,2-bis(4-(2-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(5-(2-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(6-(2-methyl)-4, 5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(7-(2-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(4-(1-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(5-(1-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(6-(1-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(7-(1-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,3- bis(4-(3-methyl)-4,5,6,7- tetrahydro ndenyl)propane, 1 ,2-bis(4-(3-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(6-(3-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(7-(3-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(4-(5-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(5-(6-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(6-(5-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(7-(5-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(4-(6-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2- bis(5-(4-methyl)-4,5,6,7- tetrahydro ndenyl)ethane, 1 ,2-bis(6-(4-methyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(7-(4-methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2- bis(4-(6-methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(5-(7-methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(6-(7-methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2- bis(7-(6-methyl H,5,6,7- tetrahydroindenyl)ethane, 2-b s(4- (2,5-di methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(4- (2,6-di methyl H,5,6,7- tetrahydroindenyl)ethane, 1 ,2- b s(4- (2,7-di methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(4- (1 ,5-dι methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(4- (1 ,6-d! methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2- b s(4- (1 ,2-d! methyl )-4.5,6,7- tetrahydroindenyl)ethane, 3-b s(4- (2,3-dι methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(4- (5,6-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2- b s(4- (5,7-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(4- (6,7-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (2,3-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (2,6-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (2,4-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (1 ,2-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (1 ,3-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (1 ,4-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (2,3-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (4,6-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b s(5- (4,7-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b is(5- (3,6-d methyl H,5,6,7- tetrahydroindenyl)ethane, 2-b is(6- (2,5-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b is(6- (2,4-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b is(6- (2,3-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b is(6- (1 ,5-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 2-b is(6- (1 ,3-d methyl H,5,6,7- tetrahydroindenyl)ethane, 2-b is(6- (1 ,2-d methyl )-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(6-(2,3-dimethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(6-(5,7-dimethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(6-(4,5-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(6-(1 ,4-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(2,5-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(2,6-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(2,4-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(1 ,5-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(1 ,6-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(1 ,2-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(2,3-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(5,6-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(4,5-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(7-(4,6-dimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, bis(4-(1 ,2,4-trimethyl)-4,5,6,7- tetrahydro ndenyl )methane, bis(7-(1 ,2,4-trimethyl)-4,5,6,7- tetrahydro ndenyl )methane, 1 ,2-bis(7-(1 ,2,4-trimethyl)-4,5,6,7- tetrahydro ndenyl )methane, bis(4-(1 ,2,7-trimethyl)-4,5,6,7- tetrahydro ndenyl )methane, bis(4-(1 ,3,5-trimethyl)-4,5,6,7- tetrahydro ndenyl )methane, 1 ,2-bis(5-(1 ,2,4-trimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(6-(1 ,2,3-trimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,3-bis(5-(5,6,7-trimethyl)-4,5,6,7- tetrahydro ndenyl )propane, 1 ,2-bis(-(4,5,7-trimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(5-(13,6,7-trimethyl)-4,5,6,7- tetrahydro ndenyl )ethane, 1 ,2-bis(4-(5,6,7-trimethyl)-4,5,6,7- tetrahydro ndenyl )methane, bis(4-(1 ,2,3,5-tetramethyl)-4,5,6,7- tetrahydro ndenyl )methane, bis(7-(1 ,2,3,4-tetramethyl)-4,5,6,7- tetrahydro ndenyl )methane, 1 ,2-bis(7-(1 ,2,3,4-tetramethyl)-4,5,6,7- tetrahydro ndenyl )ethane, bis(4-(2,5,6,7-tetramethyl)-4,5,6,7- tetrahydro ndenyl )methane, bis(4-(1 ,3,5,6-tetramethyl)-4,5,6,7- tetrahydro ndenyl )methane, 1 ,2-bis(5-(1 ,2,3,4-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2bis(6-(1 ,2,3,4-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(7-(2,4,5,6-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(4-(2,5,6,7-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(6-(3,4,5,7-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(5-(1 ,4,6,7-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, 1 ,2-bis(4-(1 ,5,6,7-tetramethyl)-4,5,6,7- tetrahydroindenyl)ethane, (4-4,5,6,7-tetrahydroindenyl)(4-(1-methyl)-4,5,6,7- tetrahydroindenyl)methane, bis(4--4,5,6,7-tetrahydroindenyl)methylmethane, bis(4-(2-methyl)-4,5,6,7-tetrahydroindenyl)dimethylmethane, (4-fluorenyl)(4- 4,5,6,7-tetrahydroindenyl)methan, 1 ,2-bis(5-4,5,6,7- tetrahydroindenyl)-1 ,2- dimethylethane, 1 ,3-bis(4-indenyl)propane
Bridged cyclopentadienyl ligands of this invention are not restricted by above examples. This invention include all compounds represented by general formula (I) by the variation of the substituents of the ligands, M, X and n. An examnple of the structure of the rac-metallocene compounds prepared according to this invention is depicted in general formula (X).
Figure imgf000013_0001
where M, X, A1, A2, and B are same as described above and R1 - R6 is are respectively same or different substituent containing 1 - 20 non-hydrogen atoms.
The structure represented by general formula (X) is very different from that of previously well-known rac-metallocene compounds where bridge is directly connected with the carbon atoms of the cyclopentadienyl ring. Furthermore, the bridge B and the position of A1 and A2 can be freely controlled. While there is conformational fluxional motion in well-known rac- ethylenebis(1-indenyl)zirconium dichloride, the rac-bridged metallocenes depicted in formula (X) have not such a conformational fluxtional motion due to the rigidity of the structure. Structure of the meso-metallocene compounds prepared according to this invention is depicted in general formula (XI).
Figure imgf000014_0001
Where M, X, A1, A2, R1 - R6 are same as described above.
There have not been reasonable way to synthesize exclusively meso- compounds but this invention gives way to synthesize exclusively meso- compounds by controlling the position of A1 and A2 and length of B so that it may impossible to form rac-compounds.
For example, (substituted) bis(5-indenyl)methane or (substituted) 1 ,2- bis(5-indenyl)ethane cannot form rac-complexes when they are transformed to metallated complexes.
Compounds depicted general formula (I) can be used for the olefin polymerization or copolymerization with cocatalysts represented by general formula (II) or (III) or (IV):
-[AI(R7)-O)m- (II)
where R7 is halogen radical, hydrocarbyl radical containing 1 - 20 carbon atoms, hydrocarbyl radical containing 1 - 20 carbon atoms substituted with halogen, m is integer more than 2, each of R7 is different or same.
N(R8)3 (III)
where N is aluminum or boron atom, R8 is same as described for R7, each R8 is same or different.
Q[N(R9)4] (IV)
where Q is inorganic or organic cation charged with +1 , N is aluminum or boron, R9 is same described for R7, and each R9 is same or different. Alkylaluminoxane compounds depicted general formula (II) can be exist as linear or cyclic or net form, each of which can be used as a single compound or a mixture. Examples of alkylaluminoxanes represented by above general formula
(II) are methylaluminoxane, ethylaluminoxane, isobutylaluminocane, butylalumninoxane, hexylalumninoxane.octylaluminoxane, ect.
Examples of alkylmetalcompouds represented by above general formula (III) are trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaiuminum, dimetylchloroaluninum, dimetylisobutylaluminum, dimetylethylaluminum, diethylchloroaluminum, triisopropylaluminum, tri-sec-butylaluminum, tricyclopenthyaiuminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethlaluminum, metyldiethylaluminum, tripenylaluminum, tri-p- tolylaiuminum, dimetylaluminummetoxide, trimetylboron, triethylboron, triisobuthylboron, tripropylboron, tributylboron, etc.
Examples of ionic compound represented by the above general formula(IV) are triethylammoniumtetraphenylboron, tributhylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimetylammonium(p-tolyl)boron, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimetylphenyl)boron, trimethylammoniumtetra(o,p-dimetylphenyl)boron, tributhylammoniumtetra(p- trifluorometylphenyl)boron, trimethylammoniumtetra(p- trichlorometylphenyl)boron, t buthylammoniumtetrapentafluorophenylboron,
N,N-diethylanilinumtetraphenylboron, N,N-diethylanilinumtetraphenylboron, N,N-diethylanilinumpentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, triphenylphosphoniumtetraphenylboron, triethylammmoniumtetraphenylaluminum, tributhylammmoniumtetraphenylaluminum, trimethylammmoniumtetraphenylaluminum, tripropylammmoniumtetraphenylaluminum, trimethylammmoniumtetra(p- tolyl)aluminum, tripropylammmoniumtetra(p-tolyl)aluminum, triethylammmoniumtetra(o,p-dimethylphenyl)aluminum, trimethylammmoniumtetra(p-trichloromethylphenyl)aluminum, tributhylammmoniumtetra(p-trichloromethylphenyl)aluminum, tributhylammoniumtetrapentaflorophenylaiuminum, N,N- diethylanilinumtetraphenylaluminum, N,N-diethylanilinumtetraphenylaluminum,
N,N-diethylanilinumtetrapentafluorophenylaluminum, diethylammoniumtetrapentafluorophenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, triethylammoniumtetraphenylboron, tributhylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra(p-tolyl)boron, tripropylammoniumtetra(p-tolyl)boron, triethylammoniumtetra(o,p-dimethylphenyl)boron, trimethylammoniumtetra(o,p- dimethylphenyl)boron, tributhylammoniumtetra(p-trifluoromethylphenyl)boron, trimethylammoniumtetra(p-trifluoromethylphenyl)boron, tributhylammoniumtetrapentafluorophenylboron, N,N- diethylanilinumtetraphenylboron, N,N- diethylanilinumtetrapentafluorophenylboron, diethylammoniumtetrapentafluorophenylboron, triphenylphorphoniumtetraphenylboron, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylboron, triphenylcarboniumtetraphenylaluminum, triphenylcarboniumtetra(p-trifluoromethylphenyl)boron, triphenylcarboniumtetrapentafluorophenylboron etc.
The polymerization of the present invention can be conducted in a conventional manner. For example, a suitable amount of an inert organic solvent and a small amount of cocatlayst are added to a glass reactor. At this stage, if a liquid monomer is to be imployed, it is introduced into the reactor together with a suitable solvent. In case of a gaseous monomer, it is charged to the reactor to a preset pressure. Then, a catalyst solution is added thereto e. g., by imploying a syringe to initiate the polymerization.
The polymerization may be conducted at a temperature ranging from 0 to 500 °C under a pressure ranging from 10 to 500 psig. The cocatalyst may be used in an amount ranging 1 to 100,000 molar equvalents based on the metallocene catalyst. Contacting order or introducing order of catalyst, cocatalyst, solvent, olefin monomer or comonomer is not limited. After polymerization for a suitable time, the polymerization reaction was quenched by adding ethanol containing hydrochloric acid. The polymer can be obtained by filtering and washing with methanol. The polymer was dried in vacuum oven.
The following example are intended to illustrate the present invention more specifically, without limiting the scope of the invention. In the examples, organic reagents and solvent used in the preparation of the catalysts and polymerization were provided from Aldrich, Strem, Sigma, Acros, B & J, Lancaster, Merck and then purified in accordance with a standard method (D. D. Perrin, "Purification of Laboratory Chemicals" 3rd ed., Pergamon Press pic: Oxford, 1988). Air sensitive compounds were prepared and handled according to the standard Shlenk technique or in a glove box under purified nitrogen or argon (D. F. Shriver, "The manipulation of air- sensitive compounds" 2nd ed., John & Wiley: New York, 1986). The alkyl aluminum compounds were purchased from Akzo and Witco. The comparative metallocene compounds were purchased from Aldrich and used without further purification. High purity gaseous monomers from Applied Gas Technology were passed through moisture and oxygen traps. Liquid monomers from Aldrich were used after a standard purification. In all steps of catalyst preparation and polymerization, air and moisture were blocked from reaction system in order to increase the reproducibility of the experiments.
The structures of catalyst synthesized were confirmed by using 270 MHz FR-NMR (Jeol Co.). The molecular weight of a polymer was measured with High Temperature Gel Permeation Chromatography (GPC) (150CV,
Waters in U.S.A) and trichlorobenzene as a solvent at a temperature of 140°C.
Example 1
Stepl : synthesis of 1 ,2-di(p-tolyl)ethane
Method 1
Two moles of 4-methyl benzyl bromide were coupled by a modification of the Burtz coupling reaction (J. March, Advanced Organic Chemistry, 449- 451 , 4th ed., 1992, A Wiley-lnterscience). Into a 250ml schlenk flask were added 12.5g of sodium, 50g of α-bromo xylene dissolved in 150ml tetrahydrofuran and then the reaction mixture were reacted 7days at argon atmosphere. Alcohol was added to quench the reaction. After water was added, the product was extracted with diethyl ether. The organic layer was collected and dried with anhydrous magnesium sulfate. After filtering to remove the magnesium sulfate, all solvent were removed by evaporation with rotary evaporator. The pure compound was obtained by recrystalization in ethanol. Yield was 26.92g (94.8 %).
1H NMR (300MHz: DMSO-d3): 57.10 (s, 8H), 2.87 (s, 4H), 2.33 (s, 6H) Method 2
This was prepared by a modification of the known method (J.H.Gerdner and P. Borgstrom, Journal of American Chemical Society, 51 ,
3375.1929). 20g of 4-methyl benzyl chloride was added dropwise to 3.8g of magnesium in 100ml of tetrahydrofuran and the reaction mixture was stirred to make Grignard reagent. This Grignard reagent was added to the same mole of silver bromide slurry in fresh dried tetrahydrofurane. After reflux for 1 hour, the reaction mixture was cooled to room temp. All solids were removed by filtration.
After water and diethyl ether were added, the organic layer was collected. After drying with anhydrous magnesium sulfate and all solvent was removed at reduced pressure. The product was purified by column chromatoghaphy. The yield was 21 g (70 %).
Method 3
20g of 4-methyl benzyl chloride is added dropwise to schlenk flask containing 3.8g of magnesium and 100ml of tetrahydrofuran to make Grignard reagent. This Grignard reagent was added to the Schlenk flask containing the same mole of 4-methyl benzylchloride in fresh dried tetrahydrofurane. After the reaction mixture was refiuxed for 3 hours, it was cooled to room temperature. Aqueous saturated ammonium chloride solution was poured, and the product was extracted with diethyl ether. The organic layer was collected and dried with anhydrous magnesium sulfate. After filtering to remove the magnesium sulfate, all solvent were removed by evaporation with rotary evaporator. The pure compound was obtained by column chromatography. Yield was 9.1 g (30 %).
Step 2: Synthesis of 1 ,2-bis(7-2,4-dimethyl)indanonyl)ethan
1 ,2-di(p-tolyl)ethan and 2-bromoisbutyryl bromide reacted to give 1 ,2- (7-(2,5-dimethyl)indanonyl)ethan by reported procedure (Stehling et al. Organometallics, 13, 968 (1994)). Pure compound was obtained by recrystalization in petroleum ether. 1H NMR(300MHz: DMSO-d3): δ 7.19-7.01(dd, 4H), 3.19-3.09(m, 2H). 2.90(s, 4H), 2.59(s, 6H), 2.61-2.31(m, 4H), 1.24-1.20(q, 6H)
Step 3: synthesis of 1 ,2-bis(7-(2,4-dimethyl)indenyl)ethan
To a flask was added successively 1 ,2-bis(7-(2,4- dimethyl)indanonyl)ethan and 40ml of tetrahydrofuran and 40ml of ethanol solution 3.5g of sodium borohydride at 0 °C. After stirring for 16 hours, 100g of ice was added. HCI was added until pH of the solution was about 1. The product was extracted with diethyl ether three times. The combined diethyl ether was washed with aqueous sodium bicarbonate. The organic layer was collected and dried with anhydrous magnesium sulfate. After filtering to remove the magnesium sulfate, all solvent were removed by evaporation with rotary evaporator to give residue, 1 ,2-bis(1-(2,4-dimethyl)indanolyl)ethan, which was used without further purification. To the flask containing the residue was added toluene and 0.2 g of mono hydrated p-tolunesulfonic acid. The reaction mixture was refluxed for 2 hours. The mixture was washed with aqueous sodium bicarbonate. The organic layer was dried with anhydrous magnesium sulfate and the solvent was removed with rotary evaporator. The product was purified by column chromatography. Yield was 92.5 % (4.16 g).
1H NMR (300MHz: CDCI3): δ 7.01-6.98(dd, 4H), 6.58(s, 2H), 3.19(s, 4H), 2.92(s, 4H), 2.37(s, 6H), 2.16(s, 6H)
Step 4: synthesis of ethylenebis(7-(2,4-dimethyl)indenyl)zirconium dichloride.
To a Schlenk flask containing 1.36g of 1 ,2-bis(7-(2,4- dimethyl)indenyl)ethan was added 20ml of freshly dried hexane, 2.5M n-butyl lithium 3.5ml in argon atmosphere. After stirring for 17 hours , 1 g of zirconium tetrachloride was added at room temp. The mixture was stirred for 18 hours. Dark gray solid was isolated by decantation of the solvent. This solid was extracted with 20ml of dichloromethan three times. The obtained yellow solution was evaporated under reduced pressure to become about 20 ml. To the solution was added hexane to recrystalize the product. Orange solid of title compound was obtained. The yield was 0.5 g.
1H NMR (300MHz: CD2CI2): δ 6.89-6.33(m, 4H), 3.39-3.19(m. 2H), 2.33- 2.30(d, 6H)
Step 5: polymerization of ethylene
To a 400 ml of glass reactor was added 200 ml hexane, 4.0 ml methylaluminoxan (MAO, toluene solution, 6.4 w% Al). At 80 °C, 0.008 mmole of ethylene bis(7-(2,4-dimethyl)indenyl)zirconium dichloride dissolved in 0.5ml toluene was added. Ethylene was fed continuously for 10 minutes under the pressure of 40 psig with vigorous stirring. 20ml of ethanol was added to finish the polymerization. 10% HCI methanol solution was poured. The solid product was collected and washed with methaol. The polymer was dried at 60 °C vacuum over. Yield was 7.45 g. Activity of catalyst was 1.9 Kg(PE) / mmol(Zr)h.
Example 2
Ethylene and nobomene copolymerization was done using the same catalyst made in step 4 of example 1.
To a 400 ml of glass reactor was added 250 ml of hexane solution of nobomene (30 g), and 4.0 ml of methylaluminoxan (MAO, toluene solution, 6.4 w % Al). At 80 °C, 0.008 mmole of ethylene bis(7-(2,4- dimethyl)indenyl)zirconium dichloride dissolved in 0.5 ml toluene was added. Ethylene was fed continuously for 10 minutes under the pressure of 40 psig with vigorous stirring. 20ml of ethanol was added to finish the polymerization. 10% HCI methanol solution was poured. The solid product was collected and washed with methaol. The polymer was dried at 60 °C vacuum oven. Yield was 14.5 g. Activity of catalyst was 7.25 Kg(PE) / mmol(Zr)h.

Claims

WHAT IS CLAIMED IS:
1. The compounds represented by general formula (I):
Figure imgf000022_0001
where
M is a transition metal selected from of Group 3 or 4 or 5 or 6.
A1 and A2 are respectively and independently hydrocarbyl triradical consisted of more than two carbon atoms which are bonded to the cyclopetadienyl ring in covalently, or 0 - 10 carbon atoms including one or more of B, N, P, S, O, or Si atom, in which the triradical may have same or different substiuents containing 1 - 20 non-hydrogen atoms.
B is hydrocarbyl diradical containing 1 - 20 carbon atoms or substituted hydrocarbyl diradical containing 0 - 20 carbon atoms, B, N, P, S, O, or Si atoms in which the diradical may have same or different substituents containing 1 - 20 non-hydrogen atoms and the radicals joined to C1 and C2 to form bridge by covalent bonds.
C1 and C2 are respectively and independently triradical of cyclopentadienyl moity which is covalently bonded to two radical sites of A1 and A2 and one radical site of M, in which the triradical may have same or different substituents containing 1 - 20 non-hydrogen atoms and the substituent may be hydrocarbyl radical with 1 - 20 carbon atoms or radical containing one or more of B, N, P, S, O, or Si atoms and 1 - 20 carbon atoms.
X is respectively and independently ligand of halogen, hydrocarbyl containing 1 - 20 carbon atoms, alkoxy, aryloxy, amide, arylamide, phosphide, arylphosphide, sulfide, or arylsulfide. n is integer of 0 - 4 which depends on the oxidation state of M.
2. The method for the preparation of homopolymers or copolymers of ethylene, .. -olefin, or cycloolefin by using the compounds represented by general formula (I) as catalyst and one or more of aluminum or boron compounds as cocatalyst.
Figure imgf000023_0001
(where M, A1, A2, C1, C2, B, X, n are same as described in claim 1)
3. The method of claim 2, wherein cocatalyst is represented by general formula (II) which can be exist as linear or cyclic or netty form.
-[AI(R7)-0)m- (II)
where R7 is halogen radical, hydrocarbyl radical containing 1 - 10 carbon atoms, or hydrocarbyl radical containing 1 - 10 carbon atoms substituted with halogen, m is integer greater than 2, each of R7 is different or same.
4. The method of claim 2, wherein cocatalyst is represented by general formula (III).
N(R8)3 (III)
where N is aluminum or boron atom, R8 is halogen radical, hydrocarbyl radical containing 1 - 10 carbon atoms, hydrocarbyl radical containing 1 - 10 carbon atoms substituted with halogen, and each of R8 is same or different.
5. The method of claim 2, wherein cocatalyst is represented by general formula (VI).
Q[N(R9)4] (IV) where Q is inorganic or organic cation charged with +1 , N is aluminum or boron, R9 is halogen radical, hydrocarbyl radical containing 1 - 10 carbon atoms, hydrocarbyl radical containing 1 - 10 carbon atoms substituted with halogen, each R9 is same or different.
6. The compounds represented by general formula (X):
Figure imgf000024_0001
where
M is a transition metal selected from Group 3, 4, 5, or 6.
A1 and A2 are respectively and independently hydrocarbyl triradical consisted of more than two carbon atoms which are bonded to the cyclopetadienyl ring in covalently, or 0 - 10 carbon atoms including one or more of B, N, P, S, O, or Si atom, in which the triradical may have same or different substiuents containing 1 - 20 non-hydrogen atoms.
B is hydrocarbyl diradical containing 1 - 20 carbon atoms or substituted hydrocarbyl diradical containing 0 - 20 carbon atoms, B, N, P, S, O, or Si atoms in which the diradical may have same or different substituents containing 1 - 20 non-hydrogen atoms and the radicals joined to C1 and C2 to form bridge by covalent bonds.
R1 - C6 are respectively same or different substituent containing 1- 20 non-hydrogen atoms.
X is respectively and independently ligand of halogen, hydrocarbyl containing 1 - 20 carbon atoms, alkoxy, aryloxy, amide, arylamide, phosphide, arylphosphide, sulfide, or arylsulfide.
7. The compounds represented by general formula (X):
Figure imgf000025_0001
where M, A1 , A2, B, R1 - R6, and X is same as described in claim 6.
PCT/KR1998/000375 1997-11-24 1998-11-24 Polymerization catalyst for olefin monomers WO1999026985A1 (en)

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